Herein, we report the synthesis and structural characterization of K[(CO)Pu](μ-η-η-O)·12HO. This is the second Pu-containing addition to the previously studied alkali-metal peroxocarbonate series M[(CO)A](μ-η-η-O)·xHO (M = alkali metal; A = Ce or Pu; x = 8, 10, 12, or 18), for which only the M = Na analogue has been previously reported when A = Pu. The previously reported crystal structure for Na[(CO)Pu](μ-η-η-O)·12HO is not isomorphous with its known Ce analogue. However, a new synthetic route to these M[(CO)A](μ-η-η-O)·12HO complexes, described below, has produced crystals of Na[(CO)Ce](μ-η-η-O)·12HO that are isomorphous with the previously reported Pu analogue. Via this synthetic method, the M = Na, K, Rb, and Cs salts of M[(CO)Ce](μ-η-η-O)·xHO have also been synthesized for a systematic structural comparison with each other and the available Pu analogues using single-crystal X-ray diffraction, Raman spectroscopy, and density functional theory calculations. The Ce salts, in particular, demonstrate subtle differences in the peroxide bond lengths, which correlate with Raman shifts for the peroxide O-O stretch (O = O atoms of the peroxide bridges) with each of the cations studied: Na [1.492(3) Å/847 cm], Rb [1.471(1) Å/854 cm], Cs [1.474(1) Å/859 cm], and K [1.468(6) Å/870 cm]. The trends observed in the O-O bond distances appear to relate to supermolecular interactions between the neighboring cations.

Technetium-99 / Pertechnetate / Phosphinimines / Selective extractantsSummary. The triphenylphosphiniminium cation (Ph 3 P= NH 2 + ) was evaluated for its selectivity for the pertechnetate anion ( 99 TcO 4 − ) using both solvent extraction and solid phase extraction methods. The solid phase extraction of TcO 4 − using trimethylsilyl-protected triphenylphosphinimine coated silica gel demonstrated the selectivity of the triphenylphosphiniminium cation for TcO 4 − over a variety of inorganic (NO 3 − , Cl − , H 2 PO 4 − , HSO 4 − /SO 4 2− ) and organic (fumarate) anions in aqueous solution (> 98% extracted when at pM TcO 4 − vs. 0.15 M anion). Iodide, lactate, benzoate and acetate were able to compete with pertechnetate (only 11-83% extracted) when present in large excess (0.15 M anion vs. 10 −12 M 99m TcO 4 − ), but not when the anion was present in a 10-fold excess. The triphenylphosphiniminium cation was significantly selective for TcO 4 − over ReO 4 − , a commonly used non-radioactive analog for 99 Tc, when tracer amounts of both competed with the anions iodide, lactate, benzoate and acetate.

Technetium-99 / Pertechnetate / Phosphinimines / Sensing / FluorescenceSummary. The trimethylsilyl-protected phosphinimines (9-anthracenyl)Ph 2 P=NSiMe 3 and (1-naphthyl)Ph 2 P=NSiMe 3 and the ion pairs [(9-anthracenyl) • , Z = 4.

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